Process for breaking petroleum emulsions employing gluconic acid salts of oxyalkylated amine-modified thermoplastic phenol-aldehyde resins



Melvin De Groote, University City, Mo., assignor to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application January 26, 1953, Serial No. 333,388

36 Claims. (Cl. 252-341) The present invention is a continuation-in-part of my five co-pending applications, Serial No. 288,744, filed May 19, 1952, now abandoned; Serial No. 296,085, filed June 27, 1952, now U. S. Patent 2,679,486; Serial No. 301,805, filed July 30, 1952, now U. S. Patent 2,743,253; Serial No. 310,553, filed September 19, 1952, now U. S. Patent 2,695,889, and Serial No. 329,484, filed January 2, 1953.

My invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

My aforementioned co-pending application, Serial No. 310,553 filed September 19, 1952, is concerned with a process for breaking petroleum emulsions of the waterin-oil type characterized by subjecting the emulsion to the action of a demulsifier including certain oxyalkylated amino resin condensates therein described.

My present invention is concerned with demulsification which involves the use of the aforementioned amino oxyalkylated resin condensate in the form of a gluconic acid salt, i. e., a form in which all or part of the basic nitrogen atoms are neutralized with gluconic acid, i. e., converted into the salt of gluconic acid.

Needless to say, all that is required is to prepare the amine oxyalkylated resin condensates in the manner de scribed in the aforementioned co-pending application, and then neutralize with gluconic acid which, for practical purposes is as simple as analogous inorganic reactions.

As far as the use of the herein described products goes for purposes of resolution of petroleum emulsions of the water-in-oil type, I particularly prefer to use the gluconic acid salt of those members which have sufficient hydrophile character to meet at least the test as set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

The present invention involves the surface-activity of the gluconic acid salts, i. e., either where only one basic amino nitrogen atom is neutralized or where all basic amino nitrogen atoms are neutralized. Such gluconic acid salts may not necessarily be Xylene soluble. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a waterited States Patent soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appro priate product being examined and then mix with the equal weight of Xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For convenience, what is said hereinafter will be divided into seven parts:

Fart 1 is concerned with the general structure of the amine-modified resins which after oxyalkylation are con verted to the gluconic acid salt;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield the amine-modified resin;

Part 3 is concerned with appropriate basic secondary polyarnines free from a hydroxyl radical which may be employed in the preparation of the herein described amine-modified resins;

Part 4 is concerned with reactions involving the resin, the polyamine, and formaldehyde to produce specific products or compounds which are then subjected to oxyalkylation;

Part 5 is concerned with the oxyalkylation of the products described in Part 4 preceding;

Part 6 is concerned with the conversion of the basic oxyalkylated derivatives described in Part 5, preceding, in the corresponding salt of gluconic acid;

Part 7 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products in the form of gluconic acid salts.

PART 1 in which R represents an aliphatic hydrocarbon substituent generally having four and not over 18 carbon atoms but most preferably not over 14 carbon atoms, and n general:

ly is a small whole number varying from 1 to 4. In the resin structure it is shown as being derived from formaldehyde although obviously other aidehydes are equally satisfactory. The amine residue in the above structure is derived from a non-hydroxylated basic polyamine and usually a strongly basic polyamine having at least ue secondary amino radical and free from anyprimary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and may be indicated thus:

in which R represents any appropriate hydrocarbon radical, such as an alkyl, alicyclic, arylalkyl radical, etc., free from hydroxyl radicals, with the proviso that at least one occurrence of R contains an amino radical which is not part of a primary amino radical or part-of a substituted imidazoline radical or part of a substituted tetrahydropyrimidine radical.

Actually, what has been depicted in the formula immediately above isonly an over-simplified exemplification of that part of the polyamine which has the reactive secondary amino group. Actually, a more complete illustration is obtained by reference to substituted polyalkylene amines of the following structure:

in which R has its prior significance, R represents a hydrogen atom or radical R, D is a hydrogen atom or analkylgroup, n represents the numerals 1 to 10, and x represents a small whole number varying from 1 to 7 but generally from 1 to 3, with the proviso that the other previously stated requirements are met. See U. S. Patent No. 2,250,176, dated July 22, 1941, to Blair.

See also U. S. Patent No. 2,362,464, dated November 14, 1944,'to Britton et al., which describes alkylene diamines and polymethylene diamines having the formula where R represents an alkyl, alkenyl, cycloalkyl, or aralkyl radical, and n represents a comparatively small integer such as 1 to 8.

A further limitation in light of the required basicity is that the secondary amino radical shall not be directly joined to an aryl radical or acyl radical or some other negative radical Needless to say, what has been stated above in regard to the groups attached to nitrogen is not intended to exclude an oxygen-interrupted linkage or a ring linkage as'in the instance of compounds obtained by converting'an N-aminoalkyl-morpholine of the formula wherein n is a whole number from 2 to 12 inclusive, and the nitrogen atoms are separated by at least two carbon atoms, into a secondary amine'by means of an alkylting agent such as dimethyl sulfate, benzyl chloride, an alkyl bromide, an ester of a sulfonic acid, etc., so as to yield a compound such as The introduction of two such polyamine radicals into a comparatively small resin molecule, for instance, one having .3 to 6 phenolic nuclei as specified, alters the resultant product in a number of ways. In the first place, a basic nitrogen atom, of course adds a hydrophile effect; in the second place, depending on the size of the radical R, there may be a counterbalancing hydrophobe effect or onein which the hydrophobe effect more than counterbalances the hydrophile effect of the nitrogen atom. Finally, in such cases where R contains one or more oxygen atoms, another efiect is introduced, particularly another'hydrophile effect; 1

The resins employed as raw materials in the instant procedure are characterized by the presence of an aliphatic radical in the ortho or para position, i. e., the

' phenols themselves are difunctional phenols.

The resins herein employed contain only two terminal groups wh ch are reactive to formaldehyde, i. e.,. they are difunctional from the standpoint of methylol-forming reactions. As is well known, although one may start with difunctional phenols, and depending on the procedure employed, one may obtain cross-linking which indicates that one or more of the phenolic nuclei have been converted from a difunctional radical to a trifunctional radical, or in terms of the resin, the molecule as a whole has a methylol-forming reactivity greater than 2. Such shift can take place after the resin has been formed or during resin formation. Briefly, an example is simply where an alkyl radical, such as methyl, ethyl, propyl, V

butyl, or the like, shifts from an ortho position to a meta position, or from a para position to a meta position. For instance, in the case of phenol-aldehyde varnish resins, one can prepare at least some in which the resins, instead of having only two points of reaction can have three, and possibly more points of reaction, with formaldehyde, or any other reactant which tends to form a methylol or substituted methylol group.

The resins herein employed are soluble in a nonoxygenated hydrocarbon solvent, such' as benzene or xylene. V I V The resins herein employed as raw materials must be comparatively low molal products having an average of 3 to 6 nuclei per resin molecule.

The condensation products here obtained, whether in the form of the free base or the salt, do not go over to the insoluble stage on heating. The condensation product obtained according to the present invention is heatstable and, in fact, one of its outstanding qualities is that it can'be subjected to oxyalkylation, particularly oxyethylation or oxypropylation, under conventional conditions, i. e., presence of an alkaline catalyst, for example,

but in any event at a temperature above C. without becoming an insoluble mass.

What has been said previously in regard to heatstability, particularly when employed as a reactant for prepara tion of derivatives, is still important from the standpoint of manufacture of the condensation products themselves insofar that in the condensation process employed in preparing the compounds described subsequently in detail, there is no objection to the employing of a temperature above the boiling point of water. As a matter of fact, all the examples included subsequently employ temperatures going up to to C.

What is said above deserves further amplification at this point for the reason that it may shorten what is said subsequently in regard to the production of the herein described condensation products. Since formaldehyde generally is employed economically in an aqueous phase (30% to 40% solution, for example) it is necessary to have manufacturing procedure which will allow reactions to take place at the interface of the two immiscible liquids, to wit, the formaldehyde solution and the resin solution, on the assumption that generally the amine will dissolve in one phase or the other. Although reactions of the kind herein described will begin at least at comparatively low temperatures, for instance, 30 C., 40 C., or 50 C., yet the reaction does not go to completion except by the use of the higher temperatures. The use of higher temperatures means, of course, that the condensation product obtained at the end of the reaction must not be heat-reactive. Of course, one can add an oxygenated solvent such as alcohol, dioxane, various ethers of glycols, or the like, and produce a homogeneous phase. If this latter procedure is employed in preparing the herein described Condensations it is purely a matter of convenience, but Whether it is or not, ultimately the temperature must still pass within the zone indicated elsewhere, i, e., somewhere above the boiling point of water unless some obvious equivalent procedure is used.

Any reference, as in the hereto appended claims to the procedure employed in the process is not intended to limit the method or order in which the reactants are added, commingled or reacted.' The procedure has been referred to as a condensation process for obvious rea- SOIlSi -As pointed out elsewhere it is my preference to dissolve the resin in a suitable solvent, add the amine, and then add the formaldehyde as a 37% solution. However, all three reactants can be added in any order. I am inclined to believe that in the presence of a basic catalyst, such as the amine employed, that the formaldehyde produces methylol groups attached to the phenolic nuclei which, in turn, react with the amine. It would be immaterial, of course, if the formaldehyde reacted with the amine so as to introduce a methylol group attached to nitrogen which, in turn, would react with the resin molecule. Also, it would be immaterial if both types of compounds were formed which reacted with each other with the evolution of a mole of formaldehyde available for further reaction. Furthermore, a reaction could take place in which three different molecules are simultaneously involved although, for theoretical reasons, that is less likely. What is said herein in this respect is simply by way of explanation to avoid any limitation in regard to the appended claims.

PART 2 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solventsoluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula R R R In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 or 12' units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., It varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 14 carbon atoms, such as a butyl, amyl, hexyl, decyl, or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be. derived from any other reactive aldehyde having 8 carbon atoms or less.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonhydroxylated secondary amine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

R\HOHHI-OHH 0H R N-o o' CN H H H H R The basic polyamine may be designated thus:

R! HN subject to what has been said previously as to the presence of at least one secondary amine radical in at least one occurrence of R with the proviso, as previously stated, that the amine radical be other than a primary, amine radical, a substituted imidazoline radical or a substituted subject to the limitation and explanation previously noted,

In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

R R R in which R' is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or Without any catalyst at all. It is preferable that the resins employed be substantially neutral. acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralizedalthough}have found In other Words, if prepared by using a strong' 7 1 that sometimes the'reaction described proceeded more rapidly in the presence of- 'a small amount of a free base. The amount may be as small asa 200th of a percent and as much as a few lOths of a percent. Sometimes moderate increase in caustic soda and caustic potash maybe used. However, the most desirable procedure in practically every case is to have the resin neutral.

, In preparing resins one does not get a single polymer, .i. e., one having just 3 units, or just 4 units, or just 5 7 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins I found no reason for using other than those which are lowest in 7 price and most. readily available commercially. For purposes'of convenience suitable resins are characterized in the following table:

i TABLE I V Moi. wt.

EX- R!!! of resin ample R Position derived n molecule number of R from (based on n+2) Prim r); Parse--. 3.5 992.5 Tertiary butyl do 3.5 882.5 Secondary butyL 3. 5 882. 5 Cyc10-hexyl 3.5 1,025.5 Tertiary amyl 3. 5 959. 5 Mixed secondary 3.5 805.5

and tertiary amyl 3.5 805.5 3.5 1,036.5 3,5 1,190 5 3.5 1,267.5 3.5 1, 344 s Dodecyl 3. 5 1, 498. 5 Tertiary butyl 3. 5 945. 5

Tertiary amyl 3. 5 1, 022.5 Nonyl 'do..-- do.. 3.5 1, 330.5 Tertiary butyl do. Butyr- 3.5 1,071.5

' aldehyde Tertiary amyl do do 3.5 1,148.5 Nony do do 3.5 1,456.5 Tertiary butyl do.' Propion- 3. 5 1,008, 5

aldehyde. Tertiary amyl '..do 3.5 1,085.5 Nonyl a; 3. 5. 1, 393. 5 Tertiary butyl 4. 2 V 906. 6

Tertiary amyl 4. 2 1, 083. 4 Nony] 4. 2 1, 430. 6 Tertiary butyl. 4. 8 l, 094. 4 Tertiary amyL. 4. 8 1,189. 6 Non 1 4.8 1, 570.4 Tertiary amyL. 1:5 604. Cyclo-hexyl. 1. 646. 0 Hexyl 1.5 653.0 1.5 688.0

2.0 092. 0 2.0 748.0 Cyclo-hcxyl 2. 0 7 i0. 0

PART 3 7 As has been pointed out, the amine herein employed as a reactant is a basic secondary polyamine andgpreferably a strongly basic secondary polyamine free from hydroxyl groups, freefrom primary amino groups, free from substituted imidazoline groups, and free from substituted tetrahydropyrimidine groups, in which the hydrocarbon radicals present, whether monovalent or divalent are aIkyL'aiicyclic, arylaikyl or heterocyclic in character. Referenceis made to applications Serial Nos. 288,744

' and 296,035 for a discussion of the basic secondary polyamines which may be usedin producing the compounds used in accordancewith the present invention. a

; -By way of example the following'formu-las are in eluded.- It will; be noted -they' include 'some polyamines 7 having a value of 2 to 4, inclusive; m represents thef which, instead of being obtained from ethylene dichloi ,.e P-Y1ene di h ri e v r th lik a ta n re n.

dichloroethyl ethers in Whichthe divalent radical has a carbon atom chain interrupted by an oxygen atom:

CH3 on,

N CzH4NC2H4N t H p H (cHslzNcflHlgoiHl i Hih CzHs' NozfilN iH-lN H/ H H CH3 GHs N C 21140 c tHrN C H 0 H;

H N pro pyleneNpropyleneN Another procedure for producing suitable polyamines is a reaction involving first an alkylene imine, such as ethylene imine or propylene imine, followed by an al-' mixed amines with an imine so as to introducea primary amino group which can be reacted with an alkylating agent, such as dimethyl sulfate. In a somewhat similar procedure the secondary amine of the kind just specified can be reacted with an alkylene oxide such as ethylene oxide, propylene oxide, or the like, and then reacted with i an imine followed by the final step noted above in order to convert theprimary amino group into a secondary amino group.

Reactions involving the same two classes of reactants previously described, i. e., a secondary amine plus an imine plus an alkylating agent, or a secondaryamine plus an alkylene oxide plus an imine plus an alkylating agent, can be applied to another class of primary amines-which are particularly desirable for the reason that they introduce a definite hydrophileeffect by virtue of an ether linkage, or repetitious ether linkage, are certain basic polyether amines of the formula:

[Rmoomionm in which x is a small wholenumber having a value of I l or more, and may be as much as 10 or 12; n is an integer numeral 1 to 2;-and m representsa number 0 to'1,-with theproviso that the sum of m plus m equals ZyandR' has its prior significance, particularly-as a hydrocarbon radical. V

The preparation of such amines has been described in the literature and particularly in two United States patcuts, to wit, U. S. Nos. 2,325,514, dated July 27, 1943, to Hester,- and 2,355,337, dated August 8, 1944, to

Spence. The latter patent describes typical haloalkyl ethers such as CHaO 11401 (|]HgGHg CH2 CHCH2OC2H4OC2N4BI 621150 CgH4O (321340 021340 CgHtCi Such haloalkyl ethers can react with ammonia, or with a primary amine such as methylamine, ethylamine, cyclohexylamine, etc., to produce a secondary amine of the kind above described, in which one of the groups attached to nitrogen is typified by R. Such haloalkyl ethers also can be reacted with ammonia to give secondary amines as described in the first of the two patents mentioned immediately preceding. Monoamines so obtained and suitable for conversion into appropriate polyamines are exemplified by Other somewhat similar secondary monoamines equally suitable for such conversion reactions in order to yield appropriate secondary amines, are those of the composition as described in U. S. Patent No. 2,375,659, dated May 8, 1945, to Jones et al. In the above formula R may be methyl, ethyl, propyl, amyl, octyl, etc.

Other suitable secondary amines which can be converted into appropriate polyamines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or for that matter, amines of the kind described in U. S. Patent No. 2,482,546, dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta phenoxyethylamine, gamma phenoxypropylamine, beta-phenoxy-alpha-methylethylamine, and beta-phenoxypropylamine.

Other secondary monoamines suitable for conversion into polyamines are the kind described in British Patent No. 456,517 and may be illustrated by Over and above the specific examples which have appeared previously, attention is directed to the fact that added suitable polyamines are shown in subsequent Table 11.

PART 4 of the cogeneric mixture except in terms of the process itself. The condensation of the resin, the amine and formaldehyde is described in detail in applications Serial Nos. 288,744 and 296,085, andreference--is-"made-to those applications for a discussion of the factors involved. j

Little more need be said as to the actual procedure employed for the preparation of the-herein described condensation products. The following example will serve by way of illustration:

Example 11) The phenol-aldehyde resin is the one that has been identified previously as Example 2a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst whichlwas completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4. nuclei, excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a; light amber color.

882 grams of the resin identified as 2a preceding were powdered and mixed with a'somewhat lesser weight 'of xylene, i. e., 600 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 30 to 35 C. and 176 grams of symmetrical dimethylethylene diamine added. The mixture was stirred vigorously and formaldehyde added slowly. In this particular instance the formaldehyde used was a 30% solution and 200 grams were employed which were added in a little short of 3 hours. The mixture was stirred vigorously and kept within a temperature range of 30 to 46 C. for about 19 hours. At the end of this time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time 'to' time. The presence of unreacted formaldehyde was noted. Any unreacted formaldehyde seemed to disappear within approximately two to three hours after refluxing, started. As soon as the odor of formaldehyde was no longer detectible the phase-separating trap was set so as to eliminate all the water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached approximately 152 C. or slightly higher. The mass was kept at this higher temperature for three to four hours and reaction stopped. During this time, any additional water which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The

overall time for reaction was somewhat less than 30 hours. In other examples, it varied from a little over 20 hours up to 36 hours. The time :can be reduced "by cutting the low temperature period to approximately 3 to 6 hours.

Note that in Table II following there are a large number of added examples illustrating the same procedure.

In each case the initial mixture was stirred and heldata fairly low temperature (30 to 40 C.) for a period of several hours.

to C., or thereabouts. Usually the mixture yielded" a clear solution by the time the bulk of the water, orfall of the water had been removed. i

Note that as pointed out previously, this proceduregi s.

illustrated by 24 examples in Table'II.

Then refluxing was employed until. the odor of formaldehyde disappeared. After the odor or,

. TABLE II 7 Strength of Reac- Reac- Max. Ex Resin Amt, Amine used and amount tormalde- Solvent used tion tion distill. No used grsl hyde soln. and amt. temp, time, temp and amt. I 0. (hrs) 0.

1b.. 2a- 882 Amine A, 176 g 30%, 200 g 26 152 2b 5a. 480 Amine A, 88 g... 30%,100 g 24 150 do .7 d0. 28 7 81 36 d0 156 do 7 32 150 200 g... d0. 21-23 30 145 37%, 100 g-" Xylene, 450 g. 20-25 148 do Xylene, 500 g; 20-27 35 143 37%, 81 g Xylene, 425 g. 20-22 V 31 145 -do .2 Xylene, 500 gm. 21-26 24 146 Xylene, 550 g.. 22-25 36 151 .Xylene, 400 g..-. 25-38 32 150 d0 21-24 30 152 Xylene, 550 g. 21-26 27 I Xylene, 400 g 20- 23 25 141 do ,22-27 29 143 Xylene 36 149 do 32 148 ylene, 30 148 do 36 152 do. Xylene, 440 g. 32 150 Amine H, 282 g. Xylene, 500 g., 21-28 25 150 Amine H, 141 g 30%, g Xylene, 350 g 21-22 28 151 7 PART 5 V I In preparing oxyalkylated derivatives .of products of'the lgind which appear as examples in Part 3, I have found it particularly advantageous to use-laboratory equipmerit which permits continuous .oxypropylation and oxyethylation. More specific reference will be made totre'atment with .glycide subsequently "in the text. The QXY-H ethylation step is, of course, the same as the oxypropylation step insofar that'two low boiling liquids are handled in; each instance.v What immediately follows refers to oxyethylation and it is understood that oxypropylation 7 can be h ndl d c n en e t n sx st ths lam fman e The oxyalkylation of the, amine resin cpndensates is 5 a tist at b pr caine wh c l? common il fid for Q the oxyalkylation of ,oxya lkylation su Pt1bl nateriaIs.v

The factors to be considered are discussed in some detail in applications Serial Nos. 301,805 and 310,553 and reference is made to those applications for a description of suitable equipment, precautions to be taken and a general discussion of operating technique. The following examples are given by way of illustration.

Example 10 resin condensate were dissolved in 6 pounds of solvent (xylene) along with one pound of finely powdered caustic soda as a catalyst. Adjustment was made in the autoclave to operate at a temperature of approximately C. to C., and'at a pressure of about 15 to 20 or 25 pounds, 25 pounds at the most. In some subsequent examples pressures up to 35 pounds were employed.

The time regulator was set so as to inject theethylene oxide in-approximately three-quarters of an hour and then continue stirring for 15 minutes or longer, a total time of one hour. The; reaction went readily and, as a matter of fact, the oxide was taken up almost immediately. Indeed the reaction was complete in less than an hour. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to excellent agitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation product, to wit, 10.82 pounds. .This represented a molal ratio of 24.6 moles of ethylene oxide per mole 0t condensate. V s

The theoretical molecular weight at the end of the reaction period was 2164. A comparatively small sample,

less than'50 grams, was withdrawn merely for'exar'ninaa in the dataor subsequent data, or in the data-presented in tabular form in'subsequent Tables 3 and 4.

The size of the autoclave employed was 25'gallons. n innume ab e Qmpa ab x l on l h i d awn a Sub n i e e atth n ea h e a d I qq le ex lk la qn on r ia e dual S m e;

was riot the case inthis particular series. Cert The amount Withdrawn.

13 examples were duplicated as hereinafter noted and subjected to oxyalkylation with a different oxide.

Example 20 This example simply illustrates the further oxyalkylation of Example 1c, preceding. As previously stated, the oxyalkylation-susceptible compound, to'wit, Example 1b, present at the beginning of the stage was obviously the same as at the end of the prior stage (Example 1c), to wit, 10.82 pounds. The amount of oxide present in the initial step was 10.82 pounds, the amount of catalyst remained the same, to wit, one pound, and the amount of solvent remained the same. Theamount of oxide added was another 10.82 pounds, all addition of oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxyethylation step the amount of oxide added was a total of 21.64 pounds and the molal ratio of ethylene oxide to resin condensate was 49.2 to 1. The theoretical molecular weight was 3246. 1

The maximum temperature during the operation was 125 C. to 130 C. The maximum pressure was in the range of 15 to 25 pounds. The time period was one and three-quarter hours. r

a Example 30 The oxyethylation was continued and the amount of oxide added again was 10.82 pounds. There was no added catalyst and no added solvent. The theroetical molecular weight at the end of the reaction period was 5410. The molal ratio of oxide to condensate was 98.4

to 1. Conditions as far as temperatre and pressure were concerned were the same as in previous examples. The time period was slightly longer, to wit, 2% hours. The

reaction unquestionably began to slow up somewhat.

Example c The oxyethylation continued with the introduction 0 another 10.82 pounds of ethylene oxide. No more solvent was introduced but .3 pound caustic soda was added. The theoretical molecular weight at the end of the agitation period was 6492, and the molal ratio of oxide to resin condensate was 123 to 1. The time period, however, dropped to 2 hours. Operating temperature and pressure remained the same as in the previous example.

Example 60 The same procedure was followed as in the previous examples. The amount of oxide added was another 10.82 pounds, bringing the total oxide introduced to 64.92 pounds. The temperature and pressure during this period were the same as before. There was no added solvent. The time period was 3 hours.

Example 70 The same procedure was followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide introduced at the end of the period was 75.74 pounds. The theoretical molecular'weight at the end of the oxyalkylation period was 8656. The time required for the oxyethylation was a bit longer than in the previous step, to wit.4 hours.

Example 8c This was the final oxyethylation in this particular series;

There was no added solvent and no added catalyst. The

total amount of oxide added at the end of this step was 86.56 pounds. The theoretical molecular weight was 9738. The molal ratio of oxide to resin condensate was 196.8 to one. Conditions as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was 5 hours. a

The same procedure as described in the previous examples was employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables III and IV, V and VI.

In substantially every case a 25-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a 15-gallon autoclave and then transferred to a 25-gallon autoclave. This 'is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables III and IV, it will be noted that compounds 10 through 40c were' obtained by the use of ethylene oxide, whereas 41c through c were obtained by the use of propylene oxide alone.

Thus, in reference to Table III it is to be noted as follows:

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible' compound, to wit, the resin condensate, is indicated in the second column.

The amount of condensate is shown in the third column.

Assuming that ethylene oxide alone is employed, as happens to be the case in Examples 1c through 40c, the amount of oxide present in the oxyalkylation derivative is shown in column 4, although in the initial step since no oxide is present there is a blank.

When ethylene oxide is used exclusively the 5th column is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent employed.

The 8th column can be ignored where a single oxide was employed.

The 9th column shows the theoretical molecular weight at the end of the oxyalkylation period.

The 10th column states the amount of condensate present in the reaction mass at the end of the period.

As pointed out previously, in this particular series the amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column 10 coincides with the figure in column 3.

Column 11 shows the amount of ethylene oxide employed in the reaction mass at the end of the particular period.

Column 12 can be ignored insofar that no propylene oxide was employed.

Column 13 shows the catalyst at the end of the reaction period.

Column 14 shows the amount of solvent at the end of the reaction period.

Column 15 shows the molal ratio of ethylene oxide to condensate.

Column 16 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table VI. It is to be noted that the first column refers to Examples 10, 2c, 30, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

' The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present, with sever l v l mes .of w ter, xylene and kerosene. It sometimes happens that although xylene in comtrated' material, when the concentrated material in turn isidiluted 'with xylene. separation takes places. 7

Referring to Table IV',Examples 410through 800 are V refers to thetotal amount of catalyst, i. e., the catalyst present from the first oxyalkylation step plus added. catalyst, if any. The same is true in regard to the sol V .vent. ,Reference to the solvent refers to the 'total solvent the counterparts of Examples 10 through 400, except that present, i. e.,,that from the first oxyalkylation step plus the oxideemployed is propylene oxide instead of ethylene added solvent, if any. 7, oxide. Therefore, asrexplained previously, four columns In this series, it will be noted-that the theoretical molecare blank, {to Wit, columns 4, 8', l1 and 15. i Q 7 ularweights are given prior to the oxyalkylation' step and 7 Reference is now made .to Table V. 'It is to be noted after the oxyalkylation step, although the value at the, these compounds are designated by d numbers, 1d, 2d, 10 end of one step is the'value at the beginning of the next 3d, etc., through and including32d. They are derived, step, except obviously'Iat the very start the value depends in turn, from compounds in" the "0 series, for example, on the theoretical molecular Weight at the end of the initial 360,400, 540 and 70c.' These compounds involve the oxyalkylation step; i. e., oxyethylation vfor 1d through f use ofbothje'thylene oxide andpropylene oxide. Since 16d, and oxypropylatiori for 17d 'through32d. 7

compounds 1c..-through 40c werei'obtained by the use, of It will be noted alsothat under the 'molal ratio the values ethylene oxide, it is obvious that those obtained from 36c of both oxides to the resin condensate are included. and 40a; involve the use of ethylene oxide first, and The data given in regard/to the operating conditions propylene oxide afterward; Inversely, those compounds is substantially the .same as before and appears in obtained from 540 and 700 obviously come from a prior Table VI.

se'riesjin which propylene oxide was used first. The products resulting from these procedures may In the'preparation of this series indicated by the small contain modest amounts, or have small amounts, of the letter d, as 1d, 2d, 3d, etc., the initial 0 series such solvents as indicated by the figures in the tables. If de- 1 as 360, 40c, 54c, and 70c; were duplicated and'the oxyalsired the solvent may be removed by distillation, and parkylation stopped at the point designated instead of being ticularly vacuum distillation. Such distillation also may 7 Carried further as y have been the Case th g nal remove traces or small amounts of uncombined oxide, if

'oxyalkylation step. Then oxyalkylation proceeded by present and volatile under the conditions employed.

using the second oxide as indicated by the previous ex- Obviously, in the use of ethylene oxideand propylene plana-tion to wit, propylene oxide in 1d through 16d, oxide in combination one neednot first use one oxide and and ethylene oxide in 17d through 32d, inclusive. then the other but one can 'mix the two oxides and thus In examining the table beginning with 1d, it will be obtain what'may be termed an indifferent oxyalkylation, noted that the initial product, i. e., 360, consisted of the i. e., no attempt to selectively add one and then the other, reaction product involving 10.82 pounds of the resin conor any other variant. V densate, 16.23 pounds of ethylene oxide, 1.0 pound Needless to say, one could start with ethylene oxide caustic soda, and 6.0 pounds of the solvent. and then use propylene oxide, and then go back to ethylene 'It is to be noted that reference to the catalyst in Table oxide; or, inversely, start with propylene oxide, then use TABLE III 7 Composition before 7 Composition at end Molai ratio Molec Ex. No. 7 wt.

0-5 0-8 Ethl. Propl. Cata- Sol- O-S1 Ethl. Propl. Cata- Sol- Ethyl. 'Propl. based cmpd., mpd., oxide, oxide, lyst, vent, cmpd., oxide, oxide, lyst, vent, oxide oxide on theex.No. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. ,lbs. to oxyto oxyoretical alkyl. alkyl. value suscept. suscept.

cmpd. cmpd.

s s s s s sws ws ssweem r eem r m m t s oeooeeo Oxyalkyltition-suscptiblts 19 ethylene oxide, and then g0 back to propylene oxide; or, one could use a combination in which butylene oxide is used. along with-either one of the twooxides just mentioned; or a combination of both of them.-

The colors of the products usually vary from a reddish amber tint to a definite-lyred, and amber. The reason is primarily that no effort is made to obtain colorless [resins initially and the resins themselves may be yellow,

amber or even dark amber. Condensation or a nitrogenous product invariablyyields .a darker product than the original resin and usuallyi-has-a reddish color. The solvent employed, if x ylenei a ds nothing to the color but one may use a darker colored aromatic petroleum solvent.

oxyalkylation generally tends to yield; lighter colored products and the more oxide employed the lighter the color of the product. Products can be prepared in which the final color is; a lighter amber with a reddish tint.

.20 Such products can be decolorizedby the use of clays, bleaching chars, etc. As far as use in demulsification is concerned, or some other industrial uses, there is no' justification for the cestofbleaehing the product.

Generally speaking, the amountof alkalinefcatalys't present is comparatively small and it need not be removed. Since the products per se are alkaline due 'to the presence of a basic nitrogen, the removal .ofithe alkaline catalyst is somewhat more difficult than. ordinarily is the case for the reason that if one adds hydrochloric acid, for example, to neutralize the alkalinity one may partially neutralize the basic nitrogen radical also. The preferred procedure is to ignore the presence of. thevv 'alkali unless it is objectionable or'else. add a stoichioa metric amount of concentrated hydrochloric acid equal;

' to the caustic soda present.

' TABLE v1 Time,

$olubllity Water Xylene 1 V Insoluble Emulllsifiablexxx V Insoluble. Do.

Kerosene TABLE VI (continued) Max. Max. Solubility Ex. temp., pres., Time, N hrs.

Water Xylene Kerosene -20 4 Insoluble Soluble..--- Insoluble.

--- -do do Do.

y Emglslfiableu do Insoluble.

do -30 3 Insouble do Do.

Do. Dispersible. Insoluble.

Disperslble.

Insoluble.

PART 6 of gluconic acid (50%) required to neutralize a certain amount of condensate; for instance, compare Example la in Table VII with Example 1b in Table II. In any 40 event, since there were available various oxyalkylated The conversion of the oxyalkylated basic condensates of the kind previously described into the corresponding salt of gluconic acid is a simple operation since it is nothing more nor less than neutralization. The condensate invariably contains two basic nitrogen atoms. One can neutralize either one or both nitrogen atoms.

Another factor which requires some consideration would be the presence of basic catalysts which were used during the oxyalkylation process. Actual tests indicate that the basicity appears to be somewhat less than would be expected, particularly in examples in which oxyalkylation is comparatively high. The usual procedure has been to add enough gluconic acid to convert the product into the salt as predetermined and then note whether or not the product showed any marked alkalinity.

If so, slightly more gluconic acid was added until the product was either just barely acid or just very moderately. alkaline. For sake of clarity this added amount of gluconic acid, it required, is ignored in subsequent Table VIII. I

Gluconic acid is available as a 50% solution. Dehydration causes decomposition. This is not true of the salts, or at least, the salts of the herein described oxyalkylated condensates. Such salts appear to be stable, or stable for all practical purposes, at least at a temperature slightly above the boiling point of water and perhaps at a temperature as high as 150 C. or thereabouts.

As has been pointed out previously the present application is a continuation-in-part of certain co-pending applications and reference is made to aforementioned copending application, Serial No. 329,484, filed January 2, 1953' The co'pendmg appilcanon Senal be reached with filtering clays, charcoals, etc. The profiled January 2, 1953, describes the neutralization of the cedure generally is, as a matter of convenience, to form non-oxyalkyl f d the salt and then dilute with a solvent if desired, using Reference now 18 m e to Table 111 6556110? is such solvent as xylene or a mixture of two-thirds xylene substantially the same as much of the data in Table II and one-third ethyl alcohol or isopropyl alcohol, to give but includes additional calculations showing the amount approximately a 50% solution. If there happened to be oxyalkylated derivatives were used for the purpose of illustrating a salt formation, all of which is illustrated in Table VIII.

Briefly stated, referring to Example 1e in Table VII it is to be noted that 1082 grams of the nonoxyalkylated condensate required 1572 grams of 50% gluconic acid for neutralization. Reference to Table VIII shows that 1082 grams of the condensate Example lb, when converted into the oxyalkylated derivative as obtained from 20, were equivalent to 3875 grams. Therefore, 3875 grams were selected as the appropriate amount of oxyalkylated material for neutralization simply for the reason that calculation was eliminated.

The oxyalkylated condensate generally is a liquid and, as a rule, contains a comparatively small amount of solvent. Note the examples in Table VIII. The solvent happened to be xylene in this instance but could have been benzene, aromatic petroleum solvent, or the like. Needless to say, the solvent could have been removed from the oxyalkylated derivative by use of vacuum dis tillation and this is particularly true if benzene happened to be thesolvent. The product obtained from oxyalkylation invariably is lighter than the initial material for 65 thereason that the condensate is dark colored and oxyalkylation simply dilutes the color. In other words, the product may be almost white, pale straw color, or an amber shade with a reddish tint.

The product either before or after neutralization can derivatives of condensates lb, and 10b these particular c any precipitate the solution is filtered.

if desired, particularly in a reflux condenser.

or a small amount of salt-like material.

23 7 If desired, the product prior to dilution could be rendered anhydrous simply by adding benzene and subjecting the mixture to reflux action under a condensate or a phase-separating trap. If there happened to be any tendency for the prodnot to separate then the solvents having hydrotropic prop- V erties, such as the diethylether of ethyleneglycol, or the like'are used. V V

The salt formation is merely a matter of agitation at room temperature, or at a somewhat higher temperature Usually agitation is continued for an hour but actually neutralization may be a matter of minutes. In some instance'after salt formation is complete and the product is diluted'to approximately 50%, I have permitted thesolution to stand for about 6 to 72 hours. Sometimes, depending on composition, there is a separation of an aqueous phase On a laboratory scale the procedure is conducted in a separatory funnel. If there is separation of an aqueousphase, or any other undesirable material, at the bottom of the separatory fun- In light of what has I'been saitlland the simplicity of salt formation it does not appear that any illust-rationf is required. 'Howeve'r, jprevious reference has been made to Table VH1; The first example in Table VIII- is--l :.x'- fample If. The following 'is more specific'da-tain're'gai'd} a, to Example-l). f" V H p .The saltwas madelfro m oxyalkylated derivative'iEr qethylen'e diamine. 882 ,grams of the iresin'were dissolved;

in approximately an equal'weight of xylene and reacted" nel it is merely discarded. The salt form, of course, 7

can be bleached in the same manner as previously described for. the 'oxyalkylated derivative. Usually the color of the salt is practically the same as the oxyalkylated derivative. For various commercial purposes in which the product is used there is no justificationfor the added cost of decolorization. The salt form can be 'd'ehydrated or rendered solvent-free by the usual procedure, i. e., vacuum distillation, after the use of a phaseseparating trap.

The product as prepared, without attempting to decolorize, eliminate any residual catalyst in the form of a salt, and without any particular effort to obtain absolute neutrality or the eqyuivalent, is more satisfactory fora numberof purposes where the material is useful, such as a demulsifier for petroleum emulsions of the water-in-oil type, or oil-'in-water type; or in the prevention of corrosion of metallic surfaces, especially ferrous surfaces; or as an asphalt additive for anti-stripping purposes.

. The condensatesvprior to oxyalkylation may be solids but are generally viscous liquids or liquids which are .al-

most solid or tacky. .Oxyalkylation reduces such materials to viscous liquids or thin liquids comparable to,

polyglycols, of course depending primarily on, the: amount of alkylene exideadded. After neutrali-zatiomthe physical characteristicsof the products areabout' the same and in the majority of cases are liquids.. Needless to say, a solvent were added', even if the material were solidinitially, it would be converted intoa liquid form.

fExqmple 1f ample 2c; Oxyalkylated derivative 2c, in turn,wasmade from condensate Iii {condensate lb, in turn,.wasl n1ade* from resin Examp'le 2a and symmetrical. dimethylated with 176 grains of the amine and 200 gramsof 30% for maldehyde. All thishas been described previously; The" weight of. the condensate on a solvent-free 'basis .was' This represented approximately 56 grams; [of basic. nitrogen. Referring to Table VIII it will be "noted that 10.82 pounds of condensate were combined, in 21.6 pounds of ethylene oxide, in combination-with 1082 grams.

6 pounds of solvent. In any event 3875 grams-of the oxyalkylated derivative 2c were placed in a laboratory device which, although made of metal, was the equivalent of a separatory funnel. To this there were added 1572 grams of glueonic acid and the mixture stirred vigorously for an hour and allowed to stand at room temperature, or thereabouts, for approximately 2 /2 days.

The slight amount of dregs at the bottom was withdrawn and the material stored as such, although it was diluted to approximately with xylene and employed in the form of a 50% solution. Afnumber of other examples are included in Table VIII.

TABLE VII Salt formation calculated on Condensate in turn derived frombasis of non-oxyalkylated Salt condensate 1 from Salt, con- 7 37% Wt. of 0 m Amt. I Amt. Amine formcondon Theo. 50% glu- N o Resin resin, Solvent sol- Amine used 1 used, aldesate on basic conic N o gms. vent, gms hyde, solventnitrogen, acid, gins. 'gms. free basis, gms. gins.

gms.

88 1 I00 580 28. 0 786' 88 .100 733 28.0 786 116 81 669 28'. 0. 786 116 81 608 28.0 .786 116 81 Y 761 28.0 786 204 2 200 l, 110 56.0 1, 572 102 2 28.0 786 102 t 100 747 28.0 786 117 81 602 37. 6 1,050 117 81 640 '37. 5. 7, 050 117 81. 794 37. 5 1,050 176 2 200 1, 082 '56. 0 1,572 116 V 81 569 28. 0.1 v393 204 Z 200 i, 56. 0 786 formaldehyde.

LFor identification of amines see notes immediately following Table 11.

Grams of oxyalkylated compound Percent which is equiv. 50 percent Oxyallryl- Conden- Amt. con- EtO PrO Solvent condento grams of congluconlc Ex. No. ated desate, densate, amt., amt, amt., sate in densate acid to rlvatlve, ex. No. lbs. lbs. lbs. lbs. oxyalkyl- 1 neutralex. No ated deize, grams rivative Oxyalkyl- Condenated comsate pound 6. 28. 0 3, 875 1, 082 1, 572 6. O 22. 0 4, 925 1, 082 1, 572 6. 0 17. 8 6, 100 l, 082 l, 572 4. 18. 7 3, 210 602 1, 050 4. 25 15. 8 3, 800 602 1, 050 4. 25 13. 6 4, 430 602 l, 050 6. 0 28. 0 3, 875 1, 082 1, 572 6. 0 22. 0 4, 925 1, 082 1, 572 6. 0 17. 8 6, 100 1, 082 1, 672 4. 25 30. 0 2, 010 602 l, 050 4. 25 23. 0 2, 620 602 1, 050 21. 64 6. 0 19. 8 5, 475 1, 082 1, 572 21. 64' 6. 0 l7. 8 6, 100 1, 082 l, 572 21. 64 6. 0 14. 2 7, 650 l, 082 1. 572 21. 64 6. 0 12. 4 750 1, 082 1, 572 21. 64 6. 0 19. 8 5, 475 1, 082 786 21. 64 6. 0 17. 8 6, 100 1, 082 786 PART 7 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of my process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents. I

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form Whichexhibits relatively limited oil-solubility. -However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000 or 1 to 30,000, or even 1 to 40,000 or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials employed as the demulsifying agent of my process.

In practicing the present process, the treating or demulsifying agent is used in the conventional way, well known to the art, described, for example, in Patent 2,626,929, dated January 27, 1953, Part 3,-and reference is made thereto for a description of conventional procedures of demulsifying, including batch, continuous, and down-the-hole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the mixture to stratify.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is the following:

Oxyalkylated derivative, for example, the product of Example 1]", 20%;

lene monosulfonic acid, 24%;.

sion to the action of a demulsifier including the gluconic' acid salts of the basic oxyalkylated products obtained in turn in the process of condensing (a) an oxyalkylationsusceptible fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular Weight corresponding to at least 7 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a 'difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said,

phenol; said resin being formed in the susbtantial absence of trifunctional phenols; said phenol being of the formula,

in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least onesecondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substitued tetrahydropyrimidine radical; and (c) formaldehyde; said condensation reaction being conducted at a V temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

2. A process for breaking petroleum emulsions of the.

V 'water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic oxyalkylated products obtained in turn in the process of condensing (a) an-oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol aldehyde resin having an average molecular weight corresponding to at least 3 and, not over 6 phenolic nuclei per'resin. molecule; said resin being difunctional only in regard to methylol-formingreactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over-8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula on i below the pyrolytic point of the reactants and resultantst of reaction; with the added provisontthat the condensation reactionbe conducted so as to produce a' significantsp'ortion 'o'fthe resultant in which each of the three reactants have contributed part of the ultimate molecule; and with the further proviso that the resinous condensation prod-- uct resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an' alpha-beta alkylene oxide having not t more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene' oxide, glycide andtmethylglycide.

3'. A process for breaking petroleum emulsionsofthe water-in-oil 'type characterized by subjecting the emulsion salts of the basic oxyalkylated products obtained in turn in the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over- 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity;.said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbonatoms and reactive toward said phenol; said resin being formed .in the substantial absence of trifunctional phenols; said phenol being ofthe for mula in which R is an aliphatic hydrocarbon radical having at 7 least 4 and not more than 24 carbon atoms and substi t tu'ted in the 2,4,6 position; (b) a basic nonhydroxylated polyarnine having at least one secondary amino group and'having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with -the"further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrirnidine radical; and ('c') formaldehyde; said condensation reaction being conducted at a to the action of a demulsifier including the gluconic acid butylene oxide, glycideand methylglycide.

temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate'molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule;'and with the further proviso that the resinous condensation product I resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of" an alpha-beta alkylene oxide having not more than 4 carbon atomsand selected from the class consist-- ring of ethylene oxide, propylene oxide, butylene oxide, 15 r glycide and methylglycide.

4. A process for breaking petroleum emulsions ofthe' water-in-oil type characterized by subjecting the emule sionto .the action of a demulsifier including the gluconic acid salts of the basic-oxyalkylated products obtained in turn inthe process of condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solvent-solu 'ble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular Weight corresponding to at least- 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction betweena difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence .of trifunctional phenols; said phenol beingof the formula I a in which R is' an aliphatic hydrocarbon radical havingat least 4-and not more than 24 carbon atoms and sub-- stituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group andhaving not over '32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline-radical and any substituted tetrahydropyrimidine radical, and (c) formaldehyde; said condensation reaction being con- 1 ducted at a temperature sufficiently high to eliminate wa:

ter and below the pyrolytic point of the reactants and resuIta-nts of reaction; with the proviso that the condensation reaction'be conducted ts o as to produce a sig-- nificant portion of the resultant-in which each of the three reactants have contributed part ofthe ultimate molecule by virtue of a formaldehyde-derived methylene- 7 bridge connecting the amino nitrogenatom of reactionwith a resin molecule; with the further proviso'that the molar ratio of reactants be approximately 1, 2 and 2 respectively; and with the final proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susceptible; followed by an oxyalkylation 'step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxid "5. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting, the'emulsion to the action of a demulsifier including the gluconic acid salts offthe basic oxyalkylated products obtained in turn in the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble,

water insoluble, low-stage phenol-aldehyde resin having an averagemolecular weight corresponding to at least 3 and not over6 phenolic nucleitresin molecule; said resin being difunctional onlyin regard to methylol-forrning reactivity; said resin being derived by reaction 29 tween a difunctional monohydric phenol and an'aldeliyde having not over 8 carbon atoms and reactivetoward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula G in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 positions; (b) a basic nonliydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of'the three re actants have contributed part of the ultimate molecuie by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure in volve the use of asolvent; and with the final proviso that the resinous condensation product resultingfr om the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide,

propylene oxide, butylene oxide, glycide and methylglycide.

6. A process for breaking petroleum emulsions of the water-'in-oil type characterized by subjecting the emulsion,

to the action of a demulsifier including the gluconicacid salts of the basic oxyalkylated products obtained in turn in the process of condensing (a) an oxyethylation-suse ceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule;

said resin being difunctional only in regard to methylolfo'rming reactivity; said resin being derivedby reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at'least 4 and not more than 24 carbon atoms and sub stituted in the 2,4,6 position; (b) a basic nonhydroxylated formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction, With the proviso that the condensatio'n reaction be conducted so as to produce a significant portion of the resultant in which each of the threereactants have contributed part of the ultimate molecule by virtue of a tormaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, Z and, 2, respectively; with'the further proviso that said. procedure involl've't-he useof a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible;'followed by an oxyalkylation step by means of an alphabeta alkylene oxide having not more than 4 carbon. atoms and's'elected "from the class consisting of ethylene oxide, propylene oxide; butylene oxide, ,glycide and methylglycide. H

7. A process for breaking petroleum emulsions of the water-in oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts offthe basic oxyalkylated products obtained in turn in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenoleformaldehyde resin having'an average molecular weight corresponding to at least 3 and not'over 6'phenolic nuclei per resin molecule; said resin being difunctional only in, regard to methylol-forming reactivityfsaidresin being derived by reaction between a difunctional monohydric phenol, and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being ofthe formula,

in which R is an aliphatic hydrocarbon radical having atleast 4 and not more than 14 carbon atoms and-substitutedin the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary; amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogenatom, and with the further proviso that the polyaminefbe free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and (c) formaldehyde; said condensation reaction being conducted product resulting from the process be heat-stablevand oxy alkylatio n-susceptible; followed by anoxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class, consistingxof ethylene oxide, propylene oxide, ,butylene oxide,glycide,andmethylglycide. I t t g 8.. A process for breaking petroleum emulsions of-the water-inoil type characterized by subjecting the emulsion tothe action of a demulsifier including the gluconic acid salts of'the basic oxyalkylated products obtained in turn in the process of condensing man in which R is an aliphatic hydrocarbon radicalhaving at 1east'4 and not more than.14 carbon atorrisatidsubstituted in the 2,4,6 position; (b) a basic nonhydrbxy lated v and methylglycide.

polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radi cal, any substituted imidazoline radical and any substituted.tetrahydopyrimidine radical, and formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below 150 C., withthe proviso that the condensation reaction be conducted so as to produce a significant portion of the resultantin which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehydederived methylene bridge connecting the amino nitrogen atom of reaction With a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the finalwater-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts ofthebasic oxyalkylated products'obtained in turn in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble,'

water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; saidresin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a para-substituted aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and (0) formaldehyde; said condensation reaction being conductedat a-temperature above the boil ingpoint of water and below 150 (2., with the proviso that the condensation reaction be conducted so as to pro duce a significant portion of the resultant in which each of the 'three reactants have contributed part of the ultimate molecule by virtue of a formaldehydederived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1,2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-sus-' ceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene 10. The process of breaking petroleum emulsions .as

, defined in claim 1 wherein the oxyalkylation step of the oxide, butylene oxide, glycide.

11. The. process of breaking petroleum emulsions as defined in claim 2 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination; ,7 1 2. The process of breaking petroleum emulsions: asv defined in claim 3 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

13. The process of breaking petroleum emulsions as defined in claim 4 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

14. The process of breaking petroleum emulsions as defined in claim 5 wherein the oxyalkylation step of'the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

15. The process of breaking petroleum emulsionsjas manufacturing process is limited to the use of both ethylene oxide and propylene-oxide in combination.

- 18. The process of breaking petroleum emulsions as defined in claim 9 wherein the oxyalkylation step of they manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

19. The process of claim 1 with the proviso that the hydrophile properties of the gluconic acid salt of the. oxyalkylated condensation product in an equal weight of, xylene are sufiicient to produce an emulsion When said; xylene solution is shaken vigorously with one to three volumes of water.

r 20. The process of claim 2 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are 'sufiicient to produce an emulsion whensaid. xylene solution is shaken vigorously with one to three volumes of water. 7

21. The process of claim 3 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weightot' xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water. 7

hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three xylene are sufiicient to produce an emulsion when said:

xylene solution is shaken vigorously with one to three. volumes of water. 1 p

25. The process of claim 7 with the proviso that the hydrophile properties of'the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.-

26. The process of claim 8 with the proviso that the" Mattie. w re.. f th FQ 9 the 22. The process of claim 4 with the proviso that the 7 33 oxyalkylated condensation product in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

27. The process of claim 9 with the proviso that the hydrophi-le properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

28. The process of claim 10 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

29. The process of claim 11 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

30. The process of claim 12 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

31. The process of claim 13 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal Weight of xylene are sufl'icient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

32. The process of claim 14 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufficient to produce an emulsion when said 34 xylene solution is shaken vigorously with one to three volumes of water.

33. The process of claim 15 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are suificient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water. a

34. The process of claim 16 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

35. The process of claim 17 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

36. The process of claim 18 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

References Cited in the file of this patent UNITED STATES PATENTS 2,031,557 Bruson Feb. 18, 1936 2,499,365 De Groote et al Mar. 7, 1950 2,535,380 Adams et al. Dec. 26, 1950 2,542,001 De Groote et al. Feb. 20, 1951 2,545,692 Gleim March 20, 1951 2,568,739 Kirkpatrick et al. Sept. 25, 1951 2,679,486 De Groote May 25, 1954 2,695,887 De Groote Nov. 30, 1954 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING THE GLUCONIC ACID SALTS OF THE BASIC OXYALKYLATED PRODUCTS OBTAINED IN TURN IN THE PROCESS OF CONDENSING (A) AN OXYALKYLATIONSUSCEPTIBLE FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBEL, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE OF MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 